This invention relates to a method of processing a light-sensitive silver halide color photographic material. More particularly, it relates to a method of processing a light-sensitive silver halide color photographic material which may not cause edge stain of color photographic paper and may improve stability of an image after the processing.
In general, light-sensitive silver halide photographic materials are, after exposure to light, processed by the steps of developing--bleaching--fixing--water washing. Such processing, however, has recently put a problem of environmental preservation or a problem of water resources which has been considered important. For this reason, methods which may reduce the large amount of washing water used have been proposed. For instance, a technique to reduce the amount of washing water by allowing the water to flow backward to washing tanks of multi-stepwise construction, is disclosed in West German Patent No. 29 20 222 as well as in a technical literature of S. R. Goldwasser, "Water flow rate in immersion-washing of motionpicture film" Jour. SMPTE, 64, 248-253, May (1955). Further, a method of carrying out stabilizing processing without substantially any water washing by omitting the washing step is disclosed in Japanese Unexamined Patent Publications No. 8543/1982, No. 14834/1983 and 134636/1983.
On the other hand, polyethylene-coated papers have been used principally as conventional color photographic papers. The polyethylene-coated papers, however, were found to become readily stained during storage because benzyl alcohol or a color developing agent contained in a color developing solution permeates to the papers, to which metal ion in an oxidizing agent or a fixing solution is adsorbed.
In particular, when a non-washing processing is carried out, it was found that, although non-colored directly after the processing, the photographic papers are extremely colored with time lapse during storage because of processing chemicals having not been removed, thereby causing the problem of edge stain. Also, it was found that, when a photographic material having been processed is stored, generation of yellow stains or discoloration of cyan dyes is disadvantageously enormous.
Moreover, since the non-washing processing using the conventional polyethylene-coated photographic paper requires a content of ferric ions in a stabilizing solution, yellow stains are liable to be formed by storing specimens after the processing.
Further, a processing solution may be a bleach-fixing solution which has both the bleaching ability and fixing ability. In a processing solution having the bleaching ability used in the processing of a light-sensitive silver halide color photographic material, inorganic oxidizing agents such as red prussiate and dichromate are widely used as an oxidizing agent to bleach silver images. However, some serious drawbacks have been pointed out in respect of the processing solution having the bleaching ability and containing these inorganic oxidizing agents. For instance, red prussiate and dichromate are relatively excellent in the bleaching power of silver images, but are liable to be decomposed by light to form cyanate ions or hexavalent chromate ions which are harmful to human bodies, and therefore by their nature are undesirable in the prevention of pollution. Also, because of very strong oxidizing powder of these oxidizing agents, it is difficult to make a silver halide solubilizing agent such as thiosulfate (a fixing agent) coexist in a same processing solution, and it is almost impossible to use these oxidizing agents in a bleach-fixing bath, thereby making it difficult to achieve the objects of making the processing speedier and simpler. Moreover, the processing solution containing these inorganic oxidizing agents has a drawback that it is difficult to recycle it without dumping the waste water after processing.
To overcome the above disadvantages, a processing solution employing, as the oxidizing agent, complex metal salts of organic acids such as aminopolycarboxylic acid metal complex salts has recently been used since it may cause less problems of pollution and meet demands for the speedy processing, the simple processing and the recycling of the waste water. However, the processing solution using the metal complex salts of organic acids is slow in the oxidizing action and therefore disadvantageous in that the bleaching rate (oxidizing rate) of silver images (metal silver) formed at a developing step is low. For instance, ethylenediaminetetraacetic acid iron (III) complex salt which is considered strongest in bleaching power among aminocarboxylic acid metal complex salts has been put into practical use in another art, but it is insufficient in the bleaching power when used for high sensitivity light-sensitive silver halide color photographic materials principally comprising silver bromide or silver iodobromide emulsion; in particular, color photographic papers containing silver iodide as silver halide, color photograpic negative films and color reversal films. This results in trace amounts of silver images remaining even after processing for a long period of time making the desilvering property inferior. This tendency is remarkable especially when the bleach-fixing solution is used because the oxidation-reduction potential is lowered in the case of the bleach-fixing solution in which the oxidizing agent is present together with thiosulfate and sulfite.